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Chapter: 2
ATOMIC STRUCTURE
INTRODUCTION
Greek philosophers concept about Atom
All kinds of matter are composed of small microscopic particles known as atoms, which is a word derived
from the Greek word “atomos” meaning indivisible. This concept of matter was known to ancient
philosophers in different parts of the world, including Democritus
(400 BC) in Greece. Science Society Relationship
John Dalton FIRE WORK DISPLAY
According to Dalton, atoms were hard solid, indivisible particles. He Candescent is the light produced from heat.
Heat caused a substance to become hot and
used atomic nature of matter to explain glow. When the temperature of fire work is
 Law of conservation of matter controlled, the desired colour can be obtained at
 Law of definite proportions proper time from the glow of certain compound
(charcoal). The heat of the metal determine the
 Law of multiple proportions colour of fire work e.g. sodium salts impart gold
Modern research or yellow colour to fire-works etc. the smoke
The modern research has shown that atoms are divisible and made effect for fire-works are produced by zinc.
up of various sub-atomic particles.
Fundamental particles
By the year 1932, it was clear that atom consisted of three sub-atomic particles electrons, protons and
neutrons. These fundamental sub-atomic particles are of much significance for a chemist, since the
arrangement of these particles within an atom determines its physical and chemical properties.

2.1. Discharge tube experiments

2.1.1. Cathode Rays-The discovery of Electron
The discovery of electron is attributed to the knowledge derived as a result of the study of the electric
discharge in the discharge tube. (Fig. 2.1)
A gas-discharge tube consists of
 A glass tube
 Metal electrodes fused in the walls

Fig. 2.1: Experimental arrangement for the study of electric discharge in gases at low pressure

 Vacuum pump to study electrical conduction through a gas at any desired value of low pressure.
The tube is filled with a gas, air or vapours of the substance to be studied, at any desired pressure. A
high voltage source is connected to the electrodes (cathode and anode).
The exact voltage required is determined by
 Length of the tube
 Pressure of gas inside the tube

Observations
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1. It was observed by William Crookes in the late 19th century, that the gas (or air) inside the tube, at
ordinary pressure, did not conduct electricity, even when the electrodes were connected to a source of
very high potential, of about 5000 volts.
2. When the pressure inside the tube was reduced by means of the vacuum pump and the tube was
connected to a high voltage of 5000–10,000 volts, an electric discharge took place, through the gas,
producing a uniform glow inside the tube. This happened at a pressure of about 0.1 mm Hg.
3. When the pressure inside the tube is further reduced to about 0.01 mm Hg, the original uniform glow
disappears and the whole tube is filled up by dark space and no luminous discharge is observed. At this
stage, the electrical resistance between the anode and the cathode becomes very high and it becomes
difficult to maintain the discharge, unless the potential difference between the anode and cathode is
very high (approximately 10,000 volts). Under this condition, some rays (faint fluorescent light) are
produced which create fluorescence on the glass wall opposite to the cathode.
4. When different gases and vapours were used in the discharge tube, under similar conditions, with
different metals used as electrodes, the same rays were produced. These rays were called cathode rays
by Goldstein (1886), since these were originated from cathode.

2.1.2. Properties of Cathode Rays

Subsequent investigations made by various scientists about the nature of the cathode rays, have suggested
the following properties for them.
(a) Charge on cathode rays
Cathode rays are negatively charged rays. J. Perrine in (1895) and JJ Thomson in (1897) showed that
when cathode rays are passed through an electric field, they are deflected towards positively charge plate
(Fig. 2.2)

Fig. 2.2: Cathode rays, deflecting in an electric field.

(b) Travel in straight line
Cathode rays travel in straight lines away from the cathode and cast shadows of opaque objects when placed
in their path. (Fig.2.3) This was the first important discovery about the nature of cathode rays made by
Hittorf in 1869.

Fig. 2.3 Cathode rays, casting shadow.

(c) Material particles
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Cathode rays are actually a bunch of moving particles with definite mass and velocity. Crookes (1870)
demonstrated that these rays could rotate a small paddle wheel, when placed in their path (Fig. 2.4)

Fig. 2.4 cathode rays, rotating a light pen wheel

This experiment shows that these rays possess kinetic energy and momentum. 'It is thus, inferred that these
rays are material in nature and has definite mass.
(d) Effect of magnetic field
JJ Thomson in 1897 demonstrated that when these rays were passed through the magnetic field, they bend
at right angle to lines joining the two poles of the magnet (Fig. 2.5).

Fig. 2.5: Cathode rays deflecting in magnetic field

(e) Production of heat

Cathode rays heat up, when strike a thin metal foil like platinum which ultimately begins to glow. This is
because the K.E possessed by these rays is converted into heat energy to heat up the metal foil.
(f) Production of X-rays
Cathode rays produce X-rays when they strike a metal target (Fig. 2.16).
(g) Ionization of gases
Cathode rays can ionize gases and also can cause a chemical change since they have a reducing effect.
Conclusion
On the basis of above experiments, it was concluded that the cathode rays are in fact negatively charged
particles emerging from cathode and were given the name "electrons” by G.J. Stoney (1874).

2.1.3. Charge to mass Ratio (e/m) of cathode rays (electrons)

The c/m ratio of electron was determined by J.J Thomson (1897). He took a special discharge tube, in
which he made arrangement to apply both the electric field and magnetic field, simultaneously.
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Fig. 2.6: Thomson's Apparatus for measuring elm ratio of electron

Observations
1. When both the fields are kept off, the electrons (cathode rays strike at P1 on the florescent screen.
2. When only the electric field is applied, they strike at P2.
3. While in the presence of magnetic field alone, they strike at P3.
4. Both the fields are adjusted in such a way that the electrons again strike at P1.
5. In this manner, the forces (i.e. electric force and magnetic force) are compared and balanced to evaluate
the e/m ratio of the electron, the final equation is
e E
= 2
m Br
Where B and E are the strengths of magnetic and electric fields, respectively and r is the radius of the
circular path of the electron in the magnetic field, which is obtained from the dimensions of the tube and
the displacement of electron spot on the fluorescent screen.
6. Using above equation, the value of e/m for electron is 1.7588×1011 C/kg
2.1.4. Charge of the Electron
J.J. Thomson was unable to determine the charge or mass of the electron separately. It was R.A Millikan
(1909), who determined the charge e of electron through his famous oil drop experiment. The calculated
charge was equal to 4.8×10-10 e.s.u. i.e. 1.6022×10-19 C

2.1.5. Mass of the Electron

The e/m ratio of electron was 1.7588×1011 C/kg and the charge was equal to 1.6022×10-19 C . Making
use of these two values the mass “m” can be calculated.
as;
e Charge on electron
=
m Mass of electron
Charge
Mass of electron =
e
m
1.6022×10-19C
Mass of electron =
1.7588×1011C/kg
m = 9.1096×10-31kg
m = 9.11×10-31kg
m = 9.11×10-28 kg
2.1.6. Canal Rays or Positive Rays - The Discovery of Proton
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While studying the cathode rays (electrons) which carried negative charge, scientists thought that there
must be some positively charged particles in the atom because matter as a whole is electrically neutral.
Having this concept in mind, E.Goldstein in 1886, took a discharge tube which contained a perforated
cathode (Fig. 2.7).

Fig. 2.7: Canal Rays (The discovery of proton)

Observations and conclusions

1. He observed that while cathode rays were traveling away from the cathode, there were some other rays
(streams of faint luminous glow), produced at the same time, moving towards cathode.
2. These rays passed through the canals of the cathode and produced sparking glow on the wall opposite
to the anode. They were called the canal rays.
3. Because of the direction of their motion, it was concluded that these rays must be positively charged.
Hence the name positive rays.
4. Canal rays or positive rays are in fact cations, produced due to collision of cathode rays with the residual
gaseous atoms in the tube. These ions, being positively charged are attracted by the cathode, some of
which pass through the holes contained in the cathode.
2.1.7. Properties of Canal Rays
a) Charge on cathode rays
Like cathode rays, canal rays also travel in straight line and when subjected to the electric or magnetic field,
they are deflected from their original path showing that they are positively charged.
b) Material in nature
They also cause mechanical motion and rotate a light pin wheel, indicating the particle (material) nature of
these rays.
c) e/m value
Their e/m ratio is always smaller than that for cathode rays and depends on the nature of gas present in the
discharge tube.
Maximum e/m value
 
The maximum e/m ratio 9.54×107 C/kg for these rays is obtained only when hydrogen gas is used in the
discharge tube. It means that the lightest (least mass) canal ray-particles are produced when hydrogen gas
is used in the tube.
Mass of positive rays from hydrogen gas
The magnitude of the positive charge of hydrogen ion was found to be 1.6022 1019 C , which is just equal
to the negative charge of an electron. Thus using e/m = 9.54×107 C/kg and e = 1.6022×10-19 C , the mass
of the canal ray-particle from hydrogen gas was found to be 1.6726×10-27 kg . This positive ray particle
was given the name proton. It was also found to be the fundamental particle of an atom.
Parts of atom
J.J. Thomson and Aston (1913), on the basis of these investigations concluded that an atom consisted of at
least two parts.
a) The electron and
b) A positive part constituting the rest of the atomic mass
2.1.8. The Discovery of Neutron (Radioactivity)
Prediction about neutron
It was believed that an atom must have the same number of electrons (-ive particles) and protons (+ive
particles) but the actual mass of the atom had always greater value than the sum of the masses of the
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electrons and the protons. This discrepancy led the scientists to conclude that atoms must also have some
heavy neutral particles in it. Rutherford in 1920 proposed that these neutral particles are present in the
nucleus (He had already discovered the nucleus in 1911, suggesting that it was positively charged). Later
in 1932, it was James Chadwick, who carried some nuclear reactions and discovered that the nucleus
contains electrically neutral particles.
Properties of neutrons
These were given the name neutrons. It was found that:
a) Penetrating power
Neutrons are highly penetrating particles.
b) Charge
They carry no charge and are not deflected by electric or magnetic field.
c) Knocking out of protons
They can knock out high speed protons from substances like paraffin, water, cellulose etc.
d) Mass of neutron
Neutron has mass 1.6749×10-27 kg and is 1842 times as heavy as electron.
e) Fundamental particle
Neutron is also a fundamental particle of matter.

By this time, the three fundamental sub-atomic particles had been discovered (Table 2.1)
Table 2.1 Characteristics of the three fundamental particles
Particle Mass (kg) Charge (C) Unit Charge Relative atomic
mass (amu)
 
Electron 9.1110 31
1.6 10 19 -1 0.00055
 
Proton 1.6726 10 27
1.6 10 19 +1 1.0073

Neutron 1.6749 10 27 -- 0 1.0087

Solar system like model

Rutherford (1911) after the discovery of the nucleus (alpha-particle scattering experiment on thin gold
foil), suggested that protons and neutrons, the two heavy particles, are present in the nucleus, which
practically constitute the whole mass of the atom while electrons are extra-nuclear particles and they revolve
around the nucleus just like the planets revolve around the sun. Atom, he thought, was a mini-solar system.

2.2. Plank's Quantum Theory

(In 1900, a German Physicist Max Plank, after studying the spectral lines obtained from hot body radiations
at different temperatures, proposed quantum theory of radiation. According to him, high energy radiations
were produced discontinuously by the particles of the hot body. Each radiation is associated with a specific
frequency, which increases with temperature.
Postulates of Plank's Quantum Theory
The main postulates of the theory are:
1. Emission or absorption of radiation
Energy emitted or absorbed by a body is not in a continuous form. It is rather, emitted or absorbed in a
discontinuous manner (Fig. 2.8) and in the form of small "unit wave" or "wave packets” or “pulse of
energy”. These discrete units are called quanta (singular; Quantum). In case of light energy, they are called
photons.
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Fig. 2.8: Heated iron ball
2. Relation between energy and frequency
Each wave packet or quantum is associated with a definite amount of energy E, which is directly
proportional to the frequency  of the radiation.
Ev
or E  hv
This is called Plank's equation where the proportionality constant, 'h' is called Plank's constant and its value
is 6.6262×10-34 Js.
3. Energy is quantized
The energy emitted or absorbed by a body is always whole number multiple of quantum i.e.
En  nhv, where n=1, 2, 3, .......etc
It means energy is quantized
2.2.1. Derivation of E=hcv
Wave length is defined as the distance between two adjacent crests or troughs, of wave.
It is expressed in nm or Å or pm
1 m = 10 9
nm =1010 Å = 1012 pm 

Fig. 2.9: A wave

Frequency v is the number of waves passing through a point in one second. Its unit is hertz  H Z  .
Wave number v is the number of wave per unit length. It is the reciprocal of wave length i.e.
1
v m1 or cm1

The frequency of a photon is inversely proportional to its wave length.
1
v

c
Or v

Where c, the proportionality constant, is called the velocity of light. Its value is 2.99×108 ms-1 . Plank's
equation is
E  hv
Substituting equation value of frequency,
c
Eh

1
But we know v

Therefore, E  hcv
Thus energy of a photon is related to the frequency, wave length and wave number.

2.3. The Bohr's Model of Atom and its Applications

Due to serious objections raised to the Rutherford's atomic model, Neil Bohr (1913), a Danish Physicist,
based his atomic model on the Plank's quantum theory. He assumed that the electron could not have just
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any energy; rather it was restricted to have a particular set of energy values, which are better known as
energy levels. That is, the energy of the electron is quantized.
Postulates of the Bohr’s theory
The main postulates of the Bohr’s theory are:
1. Electron revolves around the nucleus in fixed circular paths called the orbits (or shells). Each orbit is
associated with a definite amount of energy.
2. As long as electron remains in one of the particular orbits it does not radiate energy. The electron emits
or absorbs energy only, when it jumps from one orbit to another.
3. When the electron jumps from higher to lower orbit, it loses energy and when it jumps from lower to
higher orbit, it absorbs energy. The energy change E , is given by;
E = E 2 -E1  hv
Where E1 is the energy of lower orbit and E, is that of higher orbit; h is the Plank's constant and v is the
frequency of radiation emitted or absorbed by the electron.
4. The angular momentum (mvr) of the electron in the hydrogen atom is quantized and can have values
h
which are the whole number multiple of that is;
2π
nh
mvr  (h = Plank's constant)
2π
Where n=1, 2, 3, ....... etc., m being the mass of the electron, v, the velocity of electron and r is the radius
of the orbit.
Based on these assumptions, Bohr presented a model for hydrogen atom that can best explain the spectrum
of hydrogen atom.
Applications of Bohr's Model
2.3.1. Derivation of Radius, Energy, Frequency, Wave Length and Wave Number

1. Calculation of the radius of the Bohr's orbit

Bohr assumed that proton, being 1836 times heavier, remains stationary
with respect to electron which revolves around the nucleus in the hydrogen
atom. Let “e” be the charge of the revolving electron of mass m which moves
on the circular path (orbit) of radius “r” with velocity v. If nuclear
charge is +Ze, Z being (Proton number). Then according to Coulomb's
law, the electrostatic force of attraction (Centripetal force) between the Fig. 2.10: A Hydrogen atom
electron and the nucleus is given by:

Ze.e
FCoulombic 
r2
Ze 2
FCoulombic = k 2
r

1
Where the proportionality constant K is equal to and o is the vacuum permittivity and is a measure
4 o
of how easy it is for radiation to pass through the vacuum (free space). Its value is 8.85×10-12 C2 J -1m-1 .
Thus
Ze2
Fcoulombice 
4 o r 2
This centripetal force, provided by the Coulombic force of attraction is balanced by the centrifugal force,
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mv 2
Fcentrifugal 
r
For a stable orbit;
mv 2 Ze2

r 4 o r 2
Ze2
mv 2

4 o r
Ze2
Rearranging r
4 o mv 2
This equation shows that radius is inversely proportional to the square of the velocity of the electron. That
is to say that electron moves faster in an orbit of smaller radius.

From Bohr's postulate No. 4:

nh
mvr 
2
n2 h2
v2  2 2 2
4 m r
Substituting this value of v2 into above equation and solving for r, we get
r = Error!
Ze2× π2m2r24
r = 4π є mn2h2

Rearranging equation, we get
єn2h2
r = πmZe2
єn2h2
r = πme2 (For hydrogen, Z = 1)
The collection of parameters Error! in equation is a constant factor. The calculations show that it is equal
to 0.529×1010 m or 0.529Å.
Hence r = 0.529Å (n2)

Activity No. 1
By putting the values of n as 1, 2, 3, 4…, the radii of orbits of hydrogen atom
are Activity No 1
n=1 r1 = 0.529 Å Looking into the
n= 2 r2 = 2.11 Å values of r1, r2, r3 and
n =3 r3 = 4.75 Å r4 and r2-r1, r3-r2, etc.
n=4 r4 = 8.4 Å what do you
conclude about the
n=5 r5 = 13.22 Å
spacing between the
orbits?

The comparison shown that the distance between orbits of H-atom go on increasing
r2r1 < r3r2 < r4r3 < ……………..
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Second orbit is four times away from the nucleus than first orbit; 3rd orbit is nine times away and similarly
4th orbit is sixteen times away from the nucleus.

Example 2.1
Calculate the radius of 2nd, 3rd and 4th orbits of hydrogen atom.
Solution
We have to calculate r2 (for n = 2), r3 (for n = 3) and r4 (for n=4), using equation r = 0.529Å (n2):
r2 = 22  0.529  = 2.12 Å
r3 = 32  0.529  = 4.76 Å
r4 = 42  0.529  = 8.46Å
Practice Problem 2.1
Calculate the radius of 5th and 6th orbits of hydrogen atom.
2.3.2. Calculation of energy of the electron in an orbit
An electron in an atom possesses KE (by virtue of its motion) and PE (by virtue of its interaction with its
nucleus). The total energy E is the sum of its KE and PE.
E = KE + PE
1
Where KE  mv 2
2
and PE is equal to the work done in bringing the electron from infinity (where there is no interaction with
the nucleus) to a point at a distance r from the nucleus (where interaction exists). In doing so work must be
done, which is given by.
Work done = PE = - force × distance  r 
Ze 2
Here the force of attraction between the electron and the nucleus is as is calculated using
4 o r 2
Coloumb’s law, therefore,
Ze 2
PE   r
4 o r 2
 Ze 2
PE  
4 o r
Here the minus sign indicates that PE decreases when electron is brought from infinity to a point at a
distance 'r' from the nucleus.
Substituting values for KE and PE into E  K .E  P.E
We get
1 Ze2
E  mv 2 
2 4 o r
Ze2
Now substituting the value of mv 2 from equation mv 2  into above equation, we get
4 o r
1  Ze 2  Ze 2
E  
2  4 o r  4 o r
Ze2
E
8 o r
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єn2h2
Now putting the value of r from equation r =
πmZe2 into above equation
Z 2 me4
En  2 2 2
8 0 n h

Where En is the energy of the nth orbit.

For hydrogen atom, Z=1, so,

me4  1 
En    J / atom
8 2o h2  n2 
The term outside the brackets in above equation is constant. By inserting values for various parameters, it
comes out to be 2.18  1018 J ,
Thus

 1 
En  2.18  1018  2  J / atom
n 
 1  6.02 10
23
En  2.18  1018  2   kJ / mol
n  1000
1312.36
En   kJ / mol
n2
Activity No. 2

Substituting the values of n as 1, 2, 3, 4, 5 etc. in equation Activity No 2

You may also try for
1312.36
En   kJ / mol , we get the energy associated with an electron E2  E1, E1  E2 ,
n2
revolving in 1st, 2nd, 3rd, 4th and 5th orbits of H-atom. E4  E3 and E5  E4
1313.31 etc. to check what happens to the
E1 = 12 = 1313.13 kJ/mole successive energy levels (orbits) as
you move away from the nucleus?
1313.31
E2 = 22 = 328 kJ/mole

1313.31
E3 = = 145.92 kJ/mole
32
1313.31
E4 = = 82.08 kJ/mole
42
1313.31
E5 = = 52.53 kJ/mole
52
1313.31
E∞ = = 0 kJ/mole (Electron is free from the nucleus)
2
E2  E1 = (328.32) – (1313.31) = 984.99 kJ/mole
E3  E2 = (145.92)(328.32) = 82.49 kJ/mole
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E4  E3 = (82.08)(145.92) = 63.84 kJ/mole
E2  E1 > E3  E2 > E4  E3 > ……
E∞  E1 =0 – (1313.31) = 1313.31 kJ/mole
This value of energy (1313.315 kJ/mole) is the ionization energy of hydrogen. This is just the same as
determined experimentally.
Conclusion:
These values shows that the energy differences between adjacent orbits of Bohr’s model of hydrogen atom
go on decreasing sharply. Keep in mind that distance between adjacent orbits increases.
Practice Problem 2.2
Calculate the energy of 4th and 5th levels of the hydrogen atom.
2.3.3. Energy Difference between Two Orbits
Let E1 and E2 be the energies of lower and higher orbit respectively, then equation
1312.36
En   kJ / mol for the two orbits can be written as;
n2
me 4  Z 2 
E1   2 2  2 
8 o h  n 1 
me4  Z 2 
And E2    
8 2 o h 2  n 2 2 
me4 Z 2  1 1 
Therefore, E  E2  E1  2  2
 2 
8 o h  n 1 n 2 
2

For hydrogen atom, Z=1 so

 1 1 
E  2.18 1018   2  2  J/atom
n 1 n 2 
 1 1 
E  1312.36   2  2  J/atom
n 1 n 2 
Here n1 is any orbit and n2 is any higher orbit (which may or may not be adjacent orbit).
2.3.4. Calculation of frequency, wave length and wave number of an electron
Suppose an electron jumps from higher to lower orbit and emits a photon of particular wavelength.
According to Bohr’s equation of energy
Z2me4
E1=  2 2 2
8є◦ n1 h
Z2me4
E2 = 
8є◦2n22h2
E1 and E2 are the energies of electrons in n1 and n2, respectively. The energy difference between the two
can be calculated as follows;

Z2me4  1 1 
∆E = E2 E1 = 8є 2h2  2 2J
◦ n 
 1 n2 
For H-atom Z = 1
me4
Since 8є 2h2 = 2.18×1018 J (by putting the values of constants)
◦
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 1 1 
∆E= 2.18×1018   J
n 2 
2 2
 n1
Calculation of Frequency:
The energy difference between any two orbits of H-atom can be calculated where n1 is lower level and n2
is higher level. It is not necessary that n1 and n2 are adjacent orbits.
Since ∆E = hυ

me4  1 1 
Therefore hυ = 8є 2h2  2  2 

◦
 n1 n2 
me4  1 1 
υ = 8є 2h3  2  2  Hz

◦
 n1 n2 
Frequency (υ) has the units of cycles. s1 or Hz.
This equation gives us frequency of photon emitted when electron jumps from higher orbit to lower orbit
in H-atom by putting Z = 1. The frequency (υ) values go on decreasing between adjacent levels.
Calculation of Wave Number:
The wavelength (λ) or wave number (υ) of a spectral line depends on the quantity of energy emitted by the
electron.
Since υ = cv
Z2me4  1 
Therefore c
v =  2  12 
n
8є◦2h3
 1 n 2 

 Z2me4  1 
v =  2  1 2  m1
8є◦2h3c n n 2 
 1
me4
The value of the factor 8є 2h3c has been calculated to be 1.09678  107 m1
◦
(Rydberg constant)

  1 1 
Hence v = 1.09678×107  2  2  m1
 n1 n2 
Practice Problem 2.3
In a hydrogen atom, an electron jumps from 3th orbit to 1st orbit. Find out the frequency and wavelength of
the spectral line.
2.3.5. Spectrum of Hydrogen Atom
Before discussing the spectrum of hydrogen on the basis of Bohr's model, let us, first, have an overview of
the spectrum and its types.
Spectrum
Definition
“A visual display or dispersion of components of white light, when it is passed through a prism is called a
spectrum”. The study of spectrum is called spectroscopy and instrument used for analysis of spectrum is
called spectrometer.
Bending of light
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When light radiation is passed through a prism, it bends. The extent of bending depends on the frequency
(or wave length) of the photon. Radiation of high frequency (shorter wave length) bends to greater extent
and vice versa. Ordinary light which is a collection of electromagnetic radiations with all wavelengths,
when passed through a prism, splits up into radiations of different wave lengths. (Fig. 2.11)

Fig. 2.11 white light passes through a prism (a continuous spectrum)

Radio Micro waves Infrared (IR) Visible light Ultra Voilet X-rays Gamma Rays
Waves (UV)
  rays

 3 108 1106  3 108 7.6 102  1106 3.8 102  7.6 102 8  3.8 102 6 103  8  6 103 Wave
length in
nm
Frequency increases 

Wave length decreases 

Table 2.2: Various regions of spectrum

The spectrum shown in Fig. 2.11 falls in the visible region of radiations, which ranges from 400 nm to 750
nm of the wave length. A spectrum may be
(i) continuous spectrum or (ii) line spectrum
i. Continuous spectrum
A continuous spectrum is the one in which no clear boundary line can be seen between the colours. They
partially overlap upon each other and hence the radiations are not separated by any line. The spectrum given
in Fig. 2.11 is a continuous spectrum. Rainbow is also an example of continuous spectrum.
ii. Line spectrum
In this type of spectrum, there is a clear cut boundary between the colour bands. It is also called atomic
spectrum. When an element is vapourized on a flame or in an electric arc or in a discharge tube, it emits
light of a characteristic colour, by which it may be identified. Different colours represent different wave
lengths.
Origin of atomic spectrum
Atomic (line) spectrum is obtained when a gaseous or vapourized element is heated. The electrons in atoms
get energy and are excited. These electrons on de-excitation, emit radiations of characteristic colour
reflecting a particular wave length.
For example, sodium (Na) imparts yellow colour to the Bunsen flame, indicating that it absorbs (and then
emits) radiations in the region of wavelength ranging from 580 nm to 600 nm. Similarly, strontium gives
red colour and potassium (K) gives violet colour to the Bunsen flame.
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Fig. 2.12 Atomic excitation and de-excitation

The line spectrum may be
a. Line absorption spectrum
b. Line emission spectrum

a) Line Absorption spectrum

When radiations, consisting of all wavelengths are passed through a sample of a substance, it may absorb
a particular radiation. The spectrum of this radiation from which a particular radiation has been absorbed,
will show dark lines in continuous band. The is called line absorption spectrum (Fig. 2.13 a)
b) Line Emission Spectrum
When the substance, that has absorbed radiation (energy), emits it in the form of radiation and a
spectrum is obtained, it is called line emission spectrum. It consists of bright lines on a dark back
ground. (Fig. 2.13b)

Fig. 2.13: Line Spectrum of Hydrogen in the visible region

Spectral series
We are now in a position to test Bohr's theory by calculating the frequencies, wavelengths and wave
number, when electron jumps from one energy level (orbit) to another energy level and comparing these
values with the experimental values obtained from the spectrum of hydrogen atom. Fig. 2.13 will help you
in this connection. It is a line spectrum for hydrogen atom in the visible region. The different lines in this
spectrum are called the spectral lines. When the wave numbers,  of these spectral lines are compared
with those calculated from the Bohr's equation, they are in close agreement with each other. The wave
lengths of these spectral lines lies in the, visible and IR regions. These spectral lines are classified into at
least five groups, called spectral series, and are named after the discoverer of these series. They are:

1. Lyman series (U.V. region) is obtained, when electron returns to its ground state i.e. n1 = 1 from higher
energy levels (n2 = 2, 3, 4, 5 etc).
2. Balmer series (visible region) is obtained, when electron returns to the 2nd orbit. n1 = 2 from higher
energy levels (n2 = 3, 4, 5, 6 etc).
3. Paschan series (near IR region) is obtained when electron returns to the 3rd orbit i.e. n1 = 3 from
higher energy levels (n2 = 4, 5, 6, 7 etc).
4. Brackett series (mid IR region) is obtained electron returns to the 4th orbit i.e. n1 = 4 from higher
energy levels (n2 = 5, 6, 7 etc).
5. Pfund series (Far IR region) is obtained, when electron returns to the 5th orbit i.e. n2 = 5 from higher
energy levels (n2 = 6, 7 etc).
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Fig. 2.14 Spectral series hydrogen in various regions due to different electronic transitions

2.3.6. Defects of Bohr's Theory

The great success of Bohr's theory lies in its ability to predict lines in the hydrogen atom spectrum. It also
explains other hydrogen like simple ions like He + , Li ++ , Be+++ but fails to explain the following.
1. Multi-electron systems
It is unsuccessful to explain spectrum of more complicated atoms (multi electron system).
2. Fine structure of atom
It cannot explain the multiplicity of the spectral lines (fine structure of atom) observed under a high
resolving power spectrometer.
3. Zeeman effect
Bohr's theory cannot explain the effect of magnetic field (Zeeman Effect).
4. Stark effect
Bohr's theory cannot explain the effect of electric field (Stark effect) on the spectra of atoms.
5. Heisenberg's uncertainty principle
Bohr's model of atom goes against the Heisenberg's uncertainty principle.
2.4. X-Rays
2.4.1. Production, Properties and Uses of X-rays
Definition
X-rays are electromagnetic radiations of very high frequency (shorter wave lengths), which are produced
when cathode rays strike heavy metal anode.
Wavelength of X-rays
The wave length of the radiations, constituting X-rays, ranges from
0 0
10-2 A to 10+2 A  0.001 nm to 10 nm  .
Discovery
A German Physicist W.C. Roentgen (1895) discovered X-rays accidently while he was studying the
properties of cathode rays. These can be produced by several methods. For example
(1) Roentgen Method (gas tube)
(2) Coolidge Method
(3) By using betatron (an electron accelerating machine, devised by DW Kerst in 1941)

Roentgen Method:
1. The experimental setup for this method is shown in Fig. 2.15, which is a special type of discharge tube
at very low pressure of 0.001 mm Hg.
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2. A very high potential difference of about 30, 000 to 50, 000 volts is required to be applied between the
cathode and anode.
3. At a pressure as low as 0.001 mm Hg, some air molecules become ionized due to the influence of very
high electric field inside the tube.
4. The heavier positive ions are attracted towards the cathode and due to their collisions, electrons are
emitted from the cathode.
5. These electrons are then attracted towards the anode and hit it with greater momentum (velocity) gained
by acceleration, due to the high potential difference between the cathode and the anode.
6. This causes emission of X-rays from the surface of the anode.
7. The cathode is usually concave shaped with its focus on the anode so that the electrons emitted from
the cathode are focused on a small region of anode and X-rays are emitted from this small region.
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Fig. 2.15: X-rays (gas tube) developed by Roentgen

Properties of x-rays
The following are the main properties of X-rays.
1. Travel in straight line
X-rays travel in straight line like ordinary light.
2. Effect of electric field and magnetic field
They are not deflected by electric or magnetic fields, indicating that they are neutral.
3. Ionization of gases
They have the ability to ionize gases. The ionizing power depends on the intensity of the X-rays beam.
4. Fluorescence
X-rays produce fluorescence in many substances like rock salt, uranium, glass, compounds of calcium and
barium.
5. Reflection and refraction
X-rays are reflected as well as refracted.
6. Diffraction
X-rays can be diffracted by crystalline substances.
7. Penetration
X-rays can penetrate through many substances. Their penetration power is different in different substances.
8. Effect on photographic plate
X-rays can blacken the photographic plates. The extent of this property depends on the intensity of the X-
rays, falling on the plate.
Uses of X-rays
Following are the main uses of X-rays
1. Identification of bone fractures
The most important use of X-rays is perhaps, its application in the field of medicine. Because of its
differential penetrating power through the skin flesh of the body and the bone, X-rays make shadow of the
bone on the screen and are thus used to locate any fracture in the bone etc,.
2. Crystallinity of a substance
X-rays are used in the XRD (X-ray Diffraction analysis to check the crystallinity of a substance)
3. Inter ionic distance
X-rays are used in the analysis to measure spacing (inter ionic distance) between the ions of a crystalline
substance.
4. Ionization of gases
They can be used to ionize gases.
5. Structure of DNA
X-rays diffraction pattern of DNA helped Watson and Crick to work out its "double helix” structure in
1953.

2.4.2. Types of X-rays

X-rays are classified into the following three types, they are Kα, Kβ and K
Inner-Shell Transitions and Characteristic x-rays
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A hydrogen atom is a single electron atom. Its energy levels a single electron atom. Its energy levels are of
 13.6 ev 
the order of a few electron volts: E n =-   . Therefore, the hydrogen spectrum consists of lines in
 n 
2

the ultraviolet, visible and infrared regions.

A heavy atom has large atomic number Z and consists of Z number of electrons. The electrons are arranged
in Bohr's orbits n = 1.2.3.4. ..... which are respectively labeled as K, L, M and N shells. The outer shell
electrons are tightly bound to the nucleus. Now we shall explain that the inner-shell transitions emit photons
of frequency beyond the ultraviolet region and are known as X-rays.
Suppose a heavy target material is bombarded with a beam of electrons that has been accelerated by several
kev. Some of these electrons will collide with inner-shell electrons of the target and knock them out of their
respective atoms. Let a K-shell electron is knocked out from an atom creating a vacancy in the K-shell.
Then an electron from either L, M, or N-shell will quickly jump down to fill the vacancy in the K-shell
emitting the excess energy as X-ray photon. An X-ray photon due to transition from L-shell to the vacancy
in the K-shell is called K characteristic X-ray. The transitions from M- and N-shells to the K-shell give
rise to K  and K characteristic X-ray, respectively. Similarly L, M and N series characteristic X-rays,
relatively of low energy, are produced due to the ejection of electrons from L, M, and N-shells respectively.

Fig. 2.16. Creation of vacancy in the K-shell and transitions resulting in characteristic X-rays

2.4.3. X-rays and Atomic Number (Z)

X-rays are electromagnetic radiations of very high frequency. Henry Moseley in 1913, performed
experiments and showed that
 The frequencies of emitted X-rays increase regularly with the number of positive charge on the nuclei
of target elements, used as anode.
 He further noticed that frequency increases from element to element, as given in the periodic table, by
a single positive charge unit. This number of unit positive charges on the nucleus of an atom of an
element is now termed as the atomic number denoted by “Z”. Since the positive charge of the nucleus
is due to the presence of protons inside the nucleus, the number of unit positive charge will directly
indicate the number of protons. Thus the atomic number of an element is the number of protons present
in it.

2.4.4. Moseley's Experiment and Moseley's Law

The experimental set up of Moseley's experiment is shown in Fig. 2.17. He performed a number of
experiments at the University of Manchester, in 1913 and proved that positive charge in the nucleus was
the fundamental property of the element. Moseley used different X-rays tubes with anodes of different
materials and took spectrum of X-rays in each case, by allowing them to fall on a photographic plate.
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Fig. 2.17: Moseley's experiment (X-rays tube)

Observations
It was observed that
 The wave lengths of X-rays were the characteristics of each element, used as anode.
 The characteristic X-rays spectrum consists of spectral lines which can be grouped into K-series, L-
series, M-series etc.
 The number of lines in X-rays spectrum depends upon the nature of the target material (the nuclear
charge) and the excitation voltage.

Moseley's Law
Moseley showed that the square root of the frequency  of a spectral line is strictly related with the
nuclear charge (Z), given that the excitation potential is kept constant.
On the basis of results, he suggested that “the square root of the frequency  is directly proportional to
the atomic number (Z) of an element.

Mathematically,
 Z
To give more accurate results, Moseley modified this relationship as:
   Z  b
Where b is a constant and is known as screening constant. For spectral lines of K-series, b=1.
Thus   a  Z  b

Where “a” is the proportionality constant and its value depends on the metal under consideration. Above
equation is called the Moseley's law, which is very useful for the calculation of the atomic number Z, if
the frequencies of the spectral lines are known.
2.5. Quantum Numbers and Orbitals
Bohr's atomic model gives the concept of orbit which is a fixed circular path for the motion of electron
around the nucleus at a distance r, from the nucleus.
In 1924, de Broglie predicted that if radiation could exhibit both wave like and particle like properties,
then atomic particles like electron could also have wave-like properties.
He proved, theoretically, that the wavelength of these particles was inversely related to its momentum,
according to the equation.

h h
λ= 
mv momentum
De-Broglie's prediction was experimentally proved by two American Scientists, Davison and Germer in
1927.
In the year 1926, Erwin Schrodinger, an Austrian Physicist, developed an equation, called Schrodinger
wave equation. He considered the moving electron to exhibit a wavelike motion, forming a standing wave,
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in the three dimensional space around the nucleus. He thought the energies of electrons in atoms are
quantized.
Atomic orbital
It is thus possible to identify regions of space around the nucleus, where there is high probability of locating
an electron, associated with a specific energy. This space is called "atomic orbital” An atomic orbital, thus
represents "a definite region in the three dimensional space around the nucleus, where there is high
probability of finding an electron of a specific energy “E”.
Quantum numbers
Quantum numbers are certain numbers (which are a set of numerical values) that give information about
the designation (energy, shape of orbital etc.) of an electron in an atom.
There are four quantum numbers, three of which have been obtained by the solution of Schrodinger's wave
equation for hydrogen atom and the 4th one, which is called spin quantum number was discovered
independently.
The four quantum numbers are
a) Principal quantum number (n)
b) Azimuthal quantum number  
c) Magnetic quantum number (m)
d) Spin quantum number (s)

2.5.1. Principal Quantum Number (n)

This quantum number represents
 The main energy level or shell in which the electron is present. It is represented by “n” and can have
values;
n  1, 2, 3, 4, .....
Energy of the electron depends on the value of n, the lower the value of “n”, the lower will be the energy
of the electron and vice versa. Letter designations are also used to denote the various n-value e.g. K, L, M,
N, O, P, Q.......... shells are used for n = 1, 2, 3, 4, 5, 6, 7 etc. values, respectively. It must be noted that this
quantum number is the same as the simple whole number integer in the Bohr's atomic model.
 The value of n is associated with the size of the shell.
 The maximum number of electrons in the principal quantum number is calculated by the formula 2n2,
where n cannot have the value zero.
2.5.2. Azimuthal Quantum Number (l)
 This quantum number, which is represented by “ ” accounts for the appearance of fine lines in
hydrogen spectra.
 The spectral lines associated with the main energy level (principal quantum number) is seen to have
been split up into fine lines shown by a high resolving power spectrometer. These are called sub-shells
or energy sub-levels. So a secondary quantum number called the azimuthal quantum is also needed to
represent the sub-shells.
 The “ " may have all possible whole number values from
0 to n  1. i.e. for n  1,  0 for n  2,  0, 1, for n  3,  0, 1, 2, and for n  4,  0, 1, 2, 3

 The value of “ ” also determines the shape of the sub-shell. The shapes of sub-shell are due to
revolution of electron around the nucleus. e.g.
When = 0 then it is s-orbital and is spherical
When ( =1, the sub-shell is dumbbell shaped and is called p-sub-shell.
When = 2, the sub-shell is sausage shaped and is called the d-sub-shell.
When = 3, the sub-shell is even more complicated and is called the f-sub-shell.
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The letters s, p, d and f have been taken from the old spectroscopic terms, sharp, principal, diffused and
fundamental, respectively.

Table 2.3
n value value Sub-shell Should be No. of sub-shell
written as
1 0 s 1s 1
2 0, 1, s, p, 2s, 2p 2
3 0, 1, 2, s, p, d 3s, 3p, 3d 3
4 0, 1, 2, 3, s, p, d, f 4s, 4p, 4d, 4f 4

 The maximum of electrons in a sub-shell is given by the formula 2(2 +1). i.e; s = 2, p = 6, d = 10, and
f = 14

2.5.3. Magnetic Quantum Number (m)

 This quantum number, which is represented by “m” explains the magnetic properties of the electron.
 The magnetic field created by the charged electron can interact with the external magnetic field, due to
which the electrons in a given energy sub-level, orient themselves in certain specific regions of space
around the nucleus, called orbitals.
 The orbitals of a given sub-shell are degenerate (same energy).
 The number allowed to m, depends on the “ ” values and ranges from - through 0 to + , making a
total of (2 +1) values. i.e.
When =0, m=0 (sub-shell is “s”)
when =1, m=-1, 0, +1 (sub-shell is p, which is oriented in three directions x, y, z in space). That is
to say the sub-shell p has three degenerate orbitals Px, Py and pz, arranged in space along x, y and z
axes).
When =2, m=-2, -1, 0, +1, +2 (sub-shell is “d”, which implies that it has five space orientations due
to five "m values and are designated as dxy, dxz, dyz dx2-y2 and dz2
When =3, m= -3, -2, -1, 0, +1, +2, +3 (sub-shell is “f”, which are oriented in seven different directions
in space)
2.5.4. Spin Quantum Number (s)
 This quantum number, denoted by s, sometimes by ms, describes the spin of an electron on its axis.
 An electron may spin either in clockwise direction or in anti-clockwise direction.
 The direction of the spin can be found out by the application of an external magnetic field.
 Since an electron has equal probability to revolve clock and anti-clock wise direction around the
nucleus on its own axis.
1 1
 So the value for s may be  or  i.e.
2 2
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Fig. 2.18: Electron Spins (a) Anticlockwise (b) Clockwise

 Two electrons, residing in an orbital, with the same spin, are said to have parallel spins and are
 
represented by  , while other are said to have antiparallel or pair up spins, and are represented by

  or    .
2.5.5. Shapes of orbitals
Orbitals have no physical existence these are in fact, regions of space around the nucleus, where there is
high probability of locating an electron, with a definite amount of energy. These regions have no strict
boundaries. They can, however, be pictured by looking at the relative locations of electrons in the principal
quantum levels.
Shapes of s-orbital
The type and shape of the orbital, depends on the value of the azimuthal quantum number, “ ”. As
mentioned earlier, when =0, the energy sub level and the orbital are one and the same which is called “s”
orbital and is spherically symmetrical around the nucleus. Thus all ‘s” orbitals ( =0) are spherical in shape,
the size, however, increases with increasing “n” value. They are just like tennis ball.

Fig. 2.19: Spherical shapes of 1s and 2s orbitals.

Shapes of p-orbitals
 When =1, the sub energy level is p which consists of three orbitals for the three m values (-1, 0, +1).
 Each p-orbital has two lobes one on each side of the nucleus. The lobe of a p-orbital may be represented
by a plane that contain nucleus and is perpendicular to the corresponding axis. Such a plane is known
as nodal plane.
 Nodes may be radial node (n- -1) and angular nodes (s=0, p=1, d=2 and f=3). There is no likelihood
of finding the electron on this plane. For a Px orbital, the Y and Z planes and the nodal planes.
 The lobes of the three different p orbitals can be thought of as directed along x, y and z axes of a set of
coordinates: (Fig. 2.20).
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Fig. 2.20: Dumbbell shaped p orbitals (px, py, pz)

Shapes of d-orbitals
 When =2, the sub energy level is “d” which consists of five different orbitals (for five “m” values
i.e.  2, 1,0, 1  2  .
 They designated as d xy , d xz , d yz , d x2  y 2 and d z 2 .
 Their shapes are more complicated than those of p-orbitals, and are not like in shape.
 Three of the d-orbitals have their lobes lying on the planes xy, xz and yz and two of them have their
lobes along the axis.
 One of the d-orbital dz2, resembles p-orbital with an additional doughnut shaped space in the centre
(Fig. 2.21).

Fig. 2.21: Shapes of different d-orbitals

2.6. Electronic Configuration

Electrons in an atom live in the three dimensional space around the nucleus, called orbitals. These orbitals
are sub-divisions of the main energy level designated by the principal quantum number, n. It must be kept
in mind that all orbitals like s, px , p y , Pz , d xy , d xz .... etc. can keep a maximum of two electrons while the
maximum number of electrons that can be accommodated in a shell or shell is determined by 2n2 formula,
where n=1, 2, 3 ...
Electron of the same shell (same n value) may have energies depending upon their existence in various
orbitals.
The distribution of electrons in various orbitals (or orbits) of an atom is called electronic configuration.
Certain rules govern these distribution, These are:

2.6.1. Aufbau Principle (The Building up Principle)

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The German word “aufbau” means building up. The electronic structure of atoms is build up following the
(n + ) rule, the Pauli's exclusion principle and the Hund's rule.

“n+l” rule
According to “n+ ” rule (aufbau principle), electrons are first filled in sub energy levels or orbital with
lower n + value. In other words, electrons are filled in different orbitals in the order of their increasing
energies. If two orbital having same n + l value, lower “n” value will have lower energy and will be filled
up first. It is to be noted here, that the notation for the electronic configuration, includes the principal
quantum number (n), the letter designation for azimuthal quantum number (s, p, d, f) and a superscript to
indicate the number of electrons in the orbital or subshell e.g;

Therefore, the order of filling various orbitals according to 'n+ ' rule would
1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, ............. etc.
Another way of determining the energy order of the various orbitals is shown in Fig. 2.22:

Fig. 2.22: Order of filling atomic orbitals

2.6.2. Pauli's Exclusion Principle

According to this principle, an orbital can accommodate a maximum of two electrons and that these two
electrons, residing in the same orbital must have opposite spin. In other words “no two electrons in an atom
can have the same set of four quantum numbers”. For example for a K shell (or 1s) electron,
 ORBIT GROUP OF COLLEGES
1
n=1, =0 and m=0, let the spin quantum number for this electron is s   , which may be indicated by
2
 
upward arrow  . If another electron is put into the same orbital 1s, then its n=1, =0, m=0 but its spin
1
quantum number must be s   . In other words, it will have opposite spin relative to the first one, and
2
may be indicated by a down words arrow    . Thus, there are two different sets of the four quantum
numbers for the two electrons, residing in the same orbital i.e.
1
n  1,  0, m  0, s    for one electron 
2
1
n  1,  0, m  0, s    for other electron 
2
Two such electrons, in the same orbital, with their spins opposite to each other, are said to be paired and
are represented by  
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2.6.3. Hund's Rule
According to this rule “if degenerate orbitals (orbitals of the same energy) are available, and more than one
electron are to be filled in them, they should be placed in different orbitals with the same spin, rather than
to put them in the same orbital with opposite spins”.
It is to be noted here, that different orbitals belonging to the same subshell are degenerate e.g.
2 px , 2 p y , and 2 pz are degenerate orbitals.

2.6.4. Electronic Configurations

Based on the rules discussed above of same elements, the electronic configurations of some of the elements
in the periodic table are given in Table 2.4.
Tables 2.4: Electronic Configuration of some elements

Elements Symbol Electronic Elements Symbol Electronic Configuration

Configuration Titanium Ti (22) [Ar], 4s2, 3d2
Hydrogen H (1) 1s1 Vanadium V (23) [Ar], 4s2, 3d3
Helium He (2) 1s2 Chromium Cr (24) [Ar], 4s  , 3d5
Lithium Li (3) 1s2, 2s1 Manganese Mn (25) [Ar], 4s2, 3d5
Beryllium Be (4) 1s2, 2s2 Iron Fe (26) [Ar], 4s2, 3d6
Boron B (5) 1s , 2s2, 2p1
2
Cobalt Co (27) [Ar], 4s2, 3d7
Carbon C (6) 1s2, 2s2, 2p2 Nickel Ni (28) [Ar], 4s2, 3d8
Nitrogen N (7) 1s2, 2s2, 2p3
Oxygen O (8) 1s2, 2s2, 2p4
Copper Cu (29) [Ar], 4s  , 3d10
Sodium F (9) 1s2, 2s2, 2p5 Zinc Zn (30) [Ar], 4s2, 3d10
Magnesium Ne (10) 1s2, 2s2, 2p6 Gallium Ga (31) [Ar], 4s2, 3d10, 4p1
Aluminium Na (11) [Ne], 3s1 Germanium Ge (32) [Ar], 4s2, 3d10, 4p2
Silicon Mg (12) [Ne], 3s2 Arsenic As (33) [Ar], 4s2, 3d10, 4p3
Phosphorous Al (13) [Ne], 3s2, 3p1 Selenium Se (34) [Ar], 4s2, 3d10, 4p4
Suphur Si (14) [Ne], 3s2, 3p2 Bromine Br (35) [Ar], 4s2, 3d10, 4p5
Chlorine P (15) [Ne], 3s2, 3p3 Krypton Kr (36) [Ar], 4s2, 3d10, 4p6
Argon S (16) [Ne], 3s2, 3p4 Rubidium Rb (37) [Kr], 5s1
Potassium Cl (17) [Ne], 3s2, 3p5 Strontium Sr (38) [Kr], 5s2
Calcium Ar (18) [Ne], 3s2, 3p6 Yottrium Y (39) [Kr], 5s2, 4d1
Potassium K (19) [Ar], 4s1 Zirconium Zr (40) [Kr], 5s2, 4d2
Calcium Ca (20) [Ar], 4s2
Scandium Sc (21) [Ar], 4s2, 3d1
 ORBIT GROUP OF COLLEGES
Self Assessment
1. Briefly write the Moseley experiment.
2. Explain the magnetic quantum number in detail.
3. What are the shapes of s, p and d orbitals?
4. Define Pauli’s exclusion principle and Hund’s rule.
5. What is mean by Aufbau principle?
 ORBIT GROUP OF COLLEGES
EXERCISE
Q.1 Choose the correct answer.
1. The e/m ratio of cathode rays is __ _C/kg.
A) 1.76 1023 B) 1.76 1011 C) 1.76 1031 D) 1.76 107
2. _______ determined the charge on the electron.
A) Millikan B) J.J. Thomson C) Chadwick D) Moseley
3. Neutron was discovered by ________
A) Chadwick B) Goldstein C) JJ Thomson D) de Broglie
4. The energy associated with quantum of radiation is ________
nh 1
A) h B) C) 2h D) h
2 2
What will be the wave number of a radiation with   2 10 nm ?
8
5.
8 1 1 1 1
A) 0.5 10 nm B) 10 nm C) 5 nm D) 100 nm
6. Which of the following is not electromagnetic in nature?
A) IR rays B) X-rays C) Y-rays D) cathode rays
The frequency of a green light is 6 10 Hz . Its wavelength is
14
7.
A) 500 nm B) 5 nm C) 5000 nm D) 100 nm
8. If the mass of electron is reduced to half, the Rydberg's constant.
A) becomes half B) becomes double C) remains uncharged D) becomes one fourth
9. Which of the following is the mathematical form of Moseley's law?
a b
A)   b z  a B)   a  z  b C)  z D)  z
b z
10. For which of the following species, Bohr’s theory does not apply?
A) H B) H+ C) He+ D) Li++
11. Which of the following set of four quantum numbers is correct for an electron in K-shell?
1 1
A) n  1,  0, m  0, s   B) n  2,  1, m  0, s  
2 2
1 1
C) n  1,  1, m  0, s   D) n  2,  2, m  2, s  
2 2
12. The splitting of spectral lines in the presence of magnetic field is called
A) Stark effect B) Zeeman effect C) uncertainty principle D) Hund's rule

Q.2 Answer the following questions briefly.

i How J.J. Thomson discovered the e/m ratio of the cathode rays?
Ans: See topic 2.1.3
ii Name any four properties of cathode rays.
Ans: See topic 2.1.2
o
iii Calculate the distance ( A ) between the nucleus and an electron in the 5th orbit of an excited
hydrogen atom.
Ans: Solution:
o
rn = 0.529 × n2 A
where n = 5
o
r5 = 0.529 × (5)2 A
o
r5 = 0.529 × 25 A
 ORBIT GROUP OF COLLEGES
o
r5 = 13.225 A
iv What will be the wave number    of the spectral line of an electron when it jumps from n2 = 4
to n1 = 2?
Ans: Given: n2 = 4, n1 = 2
Find: Wave number ( v ) =?
Solution:
R = 1.0974 ×107 m-1 (Rydberg Constant)
1 1
v = R  2 - 2  m-1
 n1 n 2 
 1 1  -1
v = 1.0974×107  - 2
m
  2   4  
2

1 1 
v = 1.0974×107  -  m-1
 4 16 
 4-1 
v = 1.0974×107   m -1
 16 
3
v = 1.0974×107   m -1
16 
v =1.0974×10 ×0.1875m-1
7

v =0.2057×107m-1 = 20.57×105 m-1

Wave number v = 20.57×105m-1
v How will you differentiate between a continuous and a line spectrum?
Ans: See topic 2.3.5
vi How Moseley discovered that the atomic number (Z) is the fundamental property of an element?
Ans: See topic 2.4.3
What is the frequency of a radiation with wave number   equal to 0.5 10 m ?
8 1
vii
Ans: Given: v = 0.5×108 m-1
c = 3×108 msec-1
Find: Frequency ( v ) =?
Solution:
v = vc
v = 0.5×108 m -1×3×10 8 msec -1
v = 0.5×3×108+8sec -1
v = 1.5×1016 sec 1
Frequency ( v ) = 1.5×1016sec-1
viii Calculate the wave length of an electron when it moves with the velocity of light.
Ans: Given: Velocity of light (c) = 3×108 m/sec
Find: Wavelength of an electron
(λ) = ?
Solution:
Mass of an electron = 9.11×10-31 kg
Planck’s constant (h) = 6.6262×10-34J.sec
 ORBIT GROUP OF COLLEGES
h
λ= (de.Broglie's Equation)
mc
6.6262×10-34
λ=
9.11×10-31×3×108
6.6262
λ= ×10-34 ×10+31×10-8
27.33
λ = 0.2424×10-11m
Wavelength (λ) of an electron = 0.2424×10-11m
Q.3
a) What is Plank's quantum theory? What are the postulates of this theory?
Ans: See topic 2.2
b) Prove that E  hc , where E=energy, h=plank's constant. c=velocity of light and  wave number.
Ans: See topic 2.2
c) What will be the energy of a radiation with λ=2×10 m ?
-8

Ans: Given: λ = 2×10-8m

Find: E=?
Solution:
h = 6.6262×10-34J.Sec
c = 3×108m/sec
hc
E=
λ
6.6262×10-34 J.sec×3×108 m.sec
E=
2×10-8 m
19.87×10-26
E= J
2×10-8
E = 9.935×10-26 ×108
E = 9.935×10-18J

Q.4
a) What are the postulates of Bohr's atomic model?
Ans: See topic 2.3
b) How can Bohr's model of atom be applied to hydrogen atom to calculate the radius of nth shell?
Ans: See topic 2.3.1

c) Derive expression using Bohr's model, for the energy difference  ΔE  , frequency (U) and wave
number in hydrogen atom.
Ans: See topic 2.3.3 and 2.3.4
d) How does Bohr's model explain the hydrogen spectrum?
Ans: See topic 2.3.5
e) What are the short comings of Bohr's atomic model?
Ans: See topic 2.3.6
Q.5
a) What are X-rays? How these are produced.
Ans: See topic 2.4.1
b) Enlist some characteristics of X-rays.
 ORBIT GROUP OF COLLEGES
Ans: See topic 2.4.1
Q.6 What are quantum numbers? Discuss their significance in detail.
Ans: See topic 2.5, 2.5.1, 2.5.2, 2.5.3 and 2.5.4
Q.7
a) What is an orbital? How it differs from an orbit?
Ans: Difference between orbit and orbital

Sr # Orbits Orbitals
It is a definite circular path at It is a space around the nucleus
a definite distance from the within which the probability of
1
nucleus in which electrons finding an electron is
moves. maximum.
An orbit shows an exact Orbital does not specify the
2 position of an electron in an exact position of an electron in
atom. an atom.
The maximum number of An orbital cannot accommodate
3 electrons in an orbit is given more than 2 electrons.
by 2n2.
It represents planar motion of It represents 3D motion of
4
electrons. electrons.

b) Discuss the shapes of s, p and d orbitals.

Ans: See topic 2.5.5
Q.8
a) Calculate the wave number and wave length of a photon when the electron jumps from n2 = 4 to n1
=1.
Ans: Given: n2 = 4, n1 = 1
Find: wave number ( v ) = ?
Wave length (λ) =?
Solution:
1 1
v = R  2 - 2  m-1
 n1 n 2 
 1 1  -1
v = 1.0974×107  - 2
m
 1  4  
2

1 1 
v = 1.0974×107  -  m -1
1 16 
15 
v = 1.0974×107   m -1
16 
7
v = 1.0974×10 ×0.9375
v = 1.028×107m-1
v = 1.028×107m-1
 ORBIT GROUP OF COLLEGES
1
We know that , v 

1
λ=
v
1
λ= m
1.028 107 m1
λ = 0.972×10-7m
b) To which series of spectral lines this photon belongs?
Ans: This photon belongs to Lyman series (UV region)
Q.9
a) What will be the energy (kJ/mol) of an electron residing in n = 3 in hydrogen atom?
Ans: Given: n=3
Find: Energy of electron = ?
Solution:
-1312.36
En = kJ/mol
n2
-1312.36
En = kJ/mol
 3
2

-1312.36
En = kJ/mol
9
En = -145.81 kJ/mol
E2 = -145.81 KJ/mol
b) How much energy is lost when an electron in hydrogen atom jumps from n2 = 3 to n1 =1?
Ans: Given: n2=3 to n1=1
Find: Change in energy (∆E)=?
Solution:
 1 1 
∆E = 1312.36  2 - 2  kJ/mol
 n1 n 2 
 1 1 
∆E = 1312.36  2 - 2  kJ/mol
 1  3 
1 1 
∆E = 1312.36  -  kJ/mol
1 9 
8
∆E = 1312.36   kJ/mol
9
∆E =1312.36 ×0.888 kJ/mol
∆E =1166.54 kJ/mol
∆E =1166.54 kJ/mol
PAST PAPERS
1. Which one of the following wavelength of light falls in visible range?
 ORBIT GROUP OF COLLEGES
(A) 2nm (B) 900nm (C) 100nm (D) 500nm
2. What two quantum numbers are permissible for a 3p orbital (n and l)?
(A) 2.1 (B) 3.1 (C) 2.2 (D) 3.2
3. Which of the following constitute the stream of cathode rays?
(A) protons (B) electrons (C) x-rays (D) alpha-particles
4. How many sub-shells are present in the n  3 shell?
(A) 2 (B) 1 (C) zero (D) 3
5. The azimuthally quantum number of the 17th electron of Cl atom is:
(A) 2 (B) 1 (C) zero (D) 3
6. The mass of electron is:
(A) 9.1096 ×10-25 gm (B) 9.1096×10-27 gm (C) 9.1096×10-28 gm (D) 9.1096×10-31 gm
7. Which one of the following of the visible electromagnetic wave?
(A) ultraviolet (B) microwave (C) violet (D) X-rays
8. Mass of electron is equal to:
(A) 9.11  10-19kg (B) 9.11  10-31kg (C) 9.11  10-27kg (D) 9.11  10-34kg

9. The frequency of the radio broadcasting is 105MHz. Their  will be:

(A) 285 m (B) 28.5 m (C) 2.0 m (D) 2.85 m
10. Lyman series is obtained in:
(A) visible region (B) UV region (C) IR region (D) Microwave region
11. When an electron returns to 5th orbit, we get …………… series:
(A) Balmer (B) Paschen (C) Pfund (D) Lyman
12. The splitting of spectral lines in the presence of magnetic field is called:
(A) Stark effect (B) Zeeman effect
(C) Hund’s rule (D) Uncertainty principal
13. The splitting of spectral lines in the presence of electric field is called:
(A) Stark effect (B) Zeeman effect
(C) Hund’s rule (D) Uncertainty principal
14. Paschen series obtained near ______region
(A) U.V (B) IR (C) Visible (D) Microwave
15. The total number of orbitals in the 4 orbit is ………….
th

(A) 8 (B) 4 (C) 16 (D) 12

16. The frequency of green light is 6 × 1014 Hz. Its wavelength is………..
(A) 500 nm (B) 5nm (C) 5000mn (D) 100 nm
17. Bohr’s theory can’t explain the spectrum of:
(A) H (B) He+ (C) Li++ (D) H+
18. An orbital can have the maximum number of two electrons but with opposite spin, it is called
(A) Pauli exclusion principle (B) Hund’s rule
(C) Auf bau principle (D) Le-Chatelier principle
19. Most penetrating radiation of radioactive element is:
(A) alpha-rays (B) beta-rays (C) gamma-rays (D) x-rays
20. …………… determined charge on electron.
(A) Millikan (B) J.J Thomson (C) Chadwick (D) Moseley
21. Which one of the following is not electromagnetic in nature?
(A) Gamma-rays (B) x-rays (C) beta rays (D) radio waves
22. How many sub shells are present in the n=3 shell?
(A) 4 (B) 9 (C) 2 (D) 5
23. Which one of the following is visible electromagnetic wave?
 ORBIT GROUP OF COLLEGES
(A) Violet (B) Ultraviolet (C) Microwave (D) D-rays
24. Which type of photon is the highest energy?
(A) Infrared (B) Red (C) X-rays (D) U-V
25. Neutron was discovered by ________
(A) Rutherford (B) James Chadwick (C) Max. Plank (D) Einstein
26. The wave nature of mater was proposed by ______
(A) Chadwick (B) Rutherford (C) De-Broglie (D) J.J. Thomson
27. The total no of orbital in the second orbit is _______
(A) 2 (B) 4 (C) 6 (D) 8
28. When frequency of wave is higher, then its energy will be
(A) Higher (B) Lower (C) Unknown (D) Independent
29. Which of the given is not electromagnetic in nature?
(A) γ-rays (B) X-rays (C) Cathode rays (D) IR rays
30. Which one of the following is visible Electromagnetic wave?
(A) Violet (B) Ultraviolet (C) Microwave (D) D-rays
31. Which type of photon has the highest energy?
(A) Infrared (B) Red (C) X-rays (D) UV
32. Charge to mass ratio of electron is equal to ____________
(A) E/B2r (B) E/Br (C) E/Br2 (D) E/B2r2

PRACTICE MCQS

1. The nature of positive rays depend on

(A) The nature of electrode
(B) The nature of discharge tube
(C) The nature of residual gas
(D) All of the above
2. The velocity of photon is
(A) Independent of its wavelength
(B) Depends on its wavelength
(C) Equal to square of its amplitude
(D) Depends on its source
3. The wave number of the light emitted by a certain source is 2×106m1. The wavelength
of this light will be
(A) 500 nm (B) 500 m
(C) 200 nm (D) 5 × 107m
4. Rutherford’s model of atom failed because:
(A) The atom did not have a nucleus and electrons
(B) It did not account for the attraction between protons and neutrons
(C) It did not account for the stability of the atom
(D) There is actually no space between the nucleus and the electrons.
5. Splitting of spectral lines when atoms are subjected to strong electric field is called
(A) Zeeman effect (B) Stark effect
(C) Photoelectric effect (D) Compton effect
 ORBIT GROUP OF COLLEGES
6. In the ground state of an atom, the electron is present
(A) In the nucleus (B) In the second shell
(C) Nearest to the nucleus (D) Farthest from the nucleus
7. Quantum number values for 2p orbitals are
(A) n=2, l=1 (B) n=1, l=2
(C) n=1, l=0 (D) n=2, l=0
8. Orbital having same energy is called
(A) Hybrid orbital (B) Valence orbital
(C) Degenerate orbital (D) d-orbital
9. When 6d orbital is complete, the entering electron goes into
(A) 7f (B) 7s
(C) 7p (D) 7d
10. The radius of 2nd shell of hydrogen is
(A) 0.529 Å (B) 2.116 Å
(C) 4.0 Å (D) 5.0 Å
11. Lyman series is obtained when electron in an orbit jumps from higher energy level to
(A) ground level (B) 2nd level
(C) 3rd level (D) 4th level
12. Bracket series is present in which region of light?
(A) ultra violet (B) infrared
(C) visible (D) radiofrequency region
13. Value of Rydberg constant is
(A) 1.09678 × 107 m-1 (B) 8.84 × 1012 m-1
(C) 6.62× 10-34 J (D) none
14. Splitting of spectral line when atoms are subjected to strong magnetic field is called
(A) Stark effect (B) Zeeman effect
(C) Photoelectric effect (D) Compton effect
15. An orbital can accommodate maximum electrons
(A) 2 (B) 6
(C) 10 (D) 14
16. An orbital which is spherical symmetrical is
(A) s-orbital (B) p-orbital
(C) d-orbital (D) f-orbital
17. Number of electrons in subshells in shell can be calculated by
 ORBIT GROUP OF COLLEGES
(A) 2n2 (B) 2(2l + 1)
(C) (2l + 1) (D) 2(2m + 1)
18. Total number of s-electrons present in chromium (atomic number = 24) are
(A) 8 (B) 6
(C) 7 (D) 10
19. When 3d orbital is complete, the entering electron goes to
(A) 4d (B) 5p
(C) 4p (D) 4f
20. What is the value of (n + l) for 3d sub-shell?
(A) 1 (B) 2
(C) 3 (D) 5